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Alonso E, Casas JM, Cotton FA, et al. Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory. Inorg Chem. 1999;38(22):5034-5040doi: 10.1021/ic981437z.
Alonso, E., Casas, J. M., Cotton, F. A., Feng, X., Forniés, J., Fortuño, C., & Tomas, M. (1999). Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory. Inorganic chemistry, 38(22), 5034-5040. https://doi.org/10.1021/ic981437z
Alonso, Ester, et al. "Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory." Inorganic chemistry vol. 38,22 (1999): 5034-5040. doi: https://doi.org/10.1021/ic981437z
Alonso E, Casas JM, Cotton FA, Feng X, Forniés J, Fortuño C, Tomas M. Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory. Inorg Chem. 1999 Nov 01;38(22):5034-5040. doi: 10.1021/ic981437z. PMID: 11671247.
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Inorg Chem. 1999 Nov 01;38(22):5034-5040. doi: 10.1021/ic981437z.

Synthesis and Crystal and Electronic Structures of the Dinuclear Platinum Compounds [PEtPh(3)](2)[Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)] and [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]: A Computational Study by Density Functional Theory.

Inorganic chemistry

Ester Alonso, José M. Casas, F. Albert Cotton, Xuejung Feng, Juan Forniés, Consuelo Fortuño, Milagros Tomas

Affiliations

  1. Departamento de Química Inorgánica and Instituto de Ciencia de Materiales de Aragón, Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Department of Chemistry and Laboratory for Molecular Structure and Bonding, Texas A&M University, College Station, Texas 77843.

PMID: 11671247 DOI: 10.1021/ic981437z

Abstract

The electrolytic behavior of the dinuclear complexes [NBu(4)](2)[MM'(&mgr;-PPh(2))(2)(C(6)F(5))(4)] (M = M' = Pt (1), Pd (1a); M = Pt, M' = Pd (1b)) has been studied, showing electrochemically irreversible oxidation and related reduction processes. The chemical oxidation of the binuclear compound for M = M' = Pt, results in the formation of the binuclear Pt(III) compound [Pt(2)(&mgr;-PPh(2))(2)(C(6)F(5))(4)]. The crystal structure analysis of both complexes has been carried out, showing very similar structures with similar Pt-C and Pt-P distances and analogous skeletons. However the Pt-Pt distances are very different, 3.621(1) Å for the Pt(II) compound and 2.7245(7) Å for the Pt(III) derivative (as are the parameters geometrically related to this Pt-Pt distance), suggesting that, in the Pt(III) compound, there is a strong Pt-Pt bond. Results of DFT calculations on [Pt(2)(&mgr;-PH(2))(2)(C(6)F(5))(4)](n)()(-) (n = 2, 0) agree very well with the crystallographic data and indicate that, in the Pt(III) compound, there is approximately a single sigma bond between the metal atoms.

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